Composition containing triazinyl carboxy-alkyl sulphides



Pate nted Jan. 4, 1944 UNITED STATES PATENT OFWCE' COMPOSITIONCONTAINING TRIAZINYL CARBOXY-ALKYL SULPHIDES Gaetano F. DAlelio andJames W. Underwood,

Pittsfleld, Mass, assignors to General Electric Company, a corporationof New York No Drawing. Application February 19, 1942,

Serial No. 431,540

20 Claims. (01. 260-42) filed December 4, 1941, now Patent No.2,312,699,

issued March 2, 1943, and assigned to the same assignee as the presentinvention.

The triazinyl carboxy-alkyl sulphides used in carrying the presentinvention into effect may be represented by the following generalformula:

NHR.

x BEN-("3 c-sommo'oon In the above formula'n represents an integer andis at least 1 and not more than 2, and R represents a member of theclass consisting of hydrogen and monovalent hydrocarbon and substitutedhydrocarbon radicals, more particularly halo-hydrocarbon radicals. Froma consideration of this formula it will be seen that, since n representsan integer which is 1 or 2, the linkage of the carboxy-alkyl grouping tothe sulphur atom in all cases will be alpha or beta to the carboxygrouping. It also will be observed that linkage of the triazinylgrouping to the sulphur atom is through a carbon atom.

Illustrative examples of radicals that R in the above formula mayrepresent are: aliphatic (e..g., methyl, ethyl, propyl, isopropyl,allyl, butyl, secondary butyl, isobutyl, butenyl, amyl, methallyl,tertiary-butyl, crotyl, ethallyl, heptyl, isoheptyl, octyl, decyl,isoamyl, hexyl, etc.) including cycloaliphatic (e. g., cyclopentyl,cyclopentenyl, cyclohexyLcyclohexenyl, cycloheptyl, etc.) aryl (e. g.,phenyl, diphenyl or xenyl, naphthyl, eta); aliphatic-substituted aryl(e. g.,,tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl,allylphenyl, 2-butenylpheny1, tertiary-butylphenyl,

'etc.); aryl-substituted aliphatic (e. g., henzyl,

phenylethyl, phenylisopropyl, cinnamyl, etc.); and their homologues, aswell as those groups with one or more of their hydrogen atomssubstituted by, for example, a halogen, more particularly chlorine,bromine, fluorine or iodine. Specific examples of halogeno-substitutedhydrocarbon radicals are chlbromethyl, chloroethyl, chlorophenyl,dichlorophenyl, chlorocyclohexyl,

ethyl, chlorophenyl, phenyl, chloroethyl, bromoethyL'bromopropyl,bromotolyl, iodophenyl, etc. Preferably R in Formula I is hydrogen.However, there also may be used in carrying the present invention intoeffect chemical compounds such, for instance, as those represented bythe general formulas:

and, more particularly,

i N HzN-C (Ls- 0.1%.) 00 on above azines) represented by the aboveformulas, cor- Diamino s-triazinyl carboxy-methyl sulphide4,6-di-(methylamino) s-triazinyl-Z carboxymethyl sulphide Diaminos-triazinyl alpha-(carboxy-ethyl) sul- Dhide Diamino s-triazinylbeta-(carboxy-ethyl) sulphide 4-amino fi-methylamino s-triazinyl-2carboxymethyl sulphide 4,6-di- (ethylamino) s-triazinyl-2 carboxy-methylsulphide 4,6-di-(anilino) sulphide 4,6-di- (chloroanilino) I methylsulphide 4,6-di-(cyclohexylaminol s-triaziny1-2 carboxymethyl sulphides-triazinyl-2 carboxy-methyl s-triazinyl-Z carboxy- 4,6-diaminos-triazinyl-2 alpha-(carboxy-propyl) sulphide 4,6-diamino s-triazinyl-Zbeta-(carboxy-butyl) sulphide 4,6-diamino s-triazinyl- 2alpha-(carboxy-pentyl) sulphide 4,6-diamino s-triazinyl-2beta-(carboxy-hexyl) sulphide 4-methylamino fi-toluido (carboxy-ethyl)sulphide 4-benzylamino fi-phenethylamino s-triazinyl-2 alpha-(alpha-phenyl beta-tolyl carboxy-ethyl) sulphide 4-cyclopentylamino 6xylldino s trlazinyl 2 beta-(alpha, alpha-dibutyl beta-benzylcarboXy-propyl) sulphide 4,6-diamino s-triazinyl-2 carboxy-(bromophenyl)-methyl sulphide 4,6-diamino s-triazinyl-2 beta-(alpha-chlorophenylcarboxy-butyl) sulphide Additional examples of triazinyl carboxy-alkylsulphides that may be used in practicing the present invention are givenin our above-identified copending application Serial No. 421,682.

The present invention is based on our discovery that new and valuablematerials of particular utility in the plastics and coating arts can beproduced by effecting reaction between ingredients comprisingessentially an aldehyde, including polymeric aldehydes, hydroxyaldehydesand aldehyde-addition products, and certain triazinyl carboxy-alkylsulphides, numerous examples of which have been given above and in theaforementioned copending application. These new reaction products arenot only valuable in themselves, but find particular utility whenincorporated into an acid-curing thermosetting resin, for exampleacid-curing, thermosetting phenoplasts and aminoplasts. For instance, wemay add a soluble, fusible aldehyde-reaction product of the triazinylcarboxy-alkyl sulphide to an acid-curing thermosetting resin and heatthe resulting mixture. The aldehyde-sulphide reaction productaccelerates the conversion of the acid-curing thermosetting resin to aninsoluble, infusible state. Or, we may cause the triazinyl carboxyalkylsulphide itself to react with the acid-curing thermosetting resin andthus accelerate the curing of the resin, Or, we may form a rapidlycuring resin by effecting reaction between ingredis-triazinyl-2 betaentscomprising a triazinyl carboxy-alkyl sulphide of tie kind abovementioned, an aldehyde, including polymeric aldehydes, hydroxyaldehydesand aldehyde-addition products, and a phenol (including phenol itself,cresols, xylenols, etc.), or an amino or amido compound (including iminoand imido compounds), e. g., aminotriazoles, aminodiazines,. urea,thiourea, dicyandiamide, melamine, etc.

The resin syrups and molding compositions of this invention may bestored for long periods of time Without material alteration. In markedcontrast the prior acid-curing thermosetting resins, more particularlythose containing direct or active curing catalysts, such as acids, e.g., hydrochloric, ethyl sulphuric, phthalic, chloroacetic, phosphoric.etc., lacked. time or storage stability. This necessitated early use ofthe material after incorporating the catalyst.

Further, the molding compositions of this invention cure rapidly underheat or under heat and pressure and have good plastic flow duringmolding. Hence molded articles of even the most complicated designs canbe made rapidly and economically. The cured compositions have goodcolor, excellent water resistance and surface finish and, in general,meet the strength, hardness and other requirements of the particularservice application.

In practicing the present invention the condensation between thereactants may be carried out under acid, alkaline or neutral conditionsat normal or at elevated temperatures. Any substanc or catalyst whichhas an alkaline or an acid nature may be used to obtain the acid,alkaline or neutral condition, as for example, ammonia, sodiumhydroxide, calcium hydroxide, methyl amine, diethyl amine, tributylamine, ethanol amines, tri-isopropanol amine, etc.; mixtures of suchalkaline substances; inorganic or organic acids such as hydrochloric,sulphuric, phosphoric, acetic, acrylic, crotonic, malonic, etc.;mixtures of such acids; acid salts such as sodium acid sulphate,monosodium phosphate, monosodium phthalate, etc.; basic salts such asammonium carbonate, potassium carbonate, sodium acetate, etc.; ormixtures of such salts.

We may condense the components used in practicing this invention undervarious conditions. For example, all the components may be mixedtogether and the reaction caused to proceed under acid, alkaline orneutral conditions. Or, we may form an acid-curing thermosetting resin(e. g., an acid-curing partial condensation product of ingredientscomprising a phenol and an aldehyde, an acid-curing partial condensationproduct of ingredients comprising an amidegen compound, e. g., melamine,malonic diamide, maleic diamide, urea, thiourea, etc., and an aldehyde,etc.), add the triazinyl carboxy-alkyl sulphide thereto and effectfurther condensation. Or, we may first partially condense the diamino-triazinyl carboxy-alkyl sulphide with an aidehyde under acid, alkalineor neutral conditions and then add thereto at least one otheraldehydereactable organic compound, e. g., a phenol, a urea, aniline,etc., and effect further condensation. Also, we may separately partiallycondense a diamino triazinyl carboxy-alkyl sulphide and a differentaldehyde-reactable organic compound with an aldehyde and then mix thetwo products of partial condensation and eiiect further condensationtherebetween. The components of each reaction product may be initiallycondensed under acid, alkaline or neutral conditions.

Still other ways may be employed in combining the components and inproducing the unmodified and modified condensation products of thisinvention, as readily will be understood by those skilled in the art asthe description of the invention proceeds. These condensation reactionsmay be carried out under a wide variety of time, pressure andtemperature conditions. The temperature of reaction may vary from roomtempera ture to the reflux temperature of the reactants at reduced,atmospheric or superatmospheric pressures,

In order that those skilled in the art better may understand how thepresent invention may be carried into effect, the following illustrativeexamples thereof are given. All parts are by weight.

Example 1 Parts Diamino s-triazinyl carboxy-methyl sulphide 20.0 Aqueousformaldehyde ('approx. 37.1%

HCHO) 81.0

tion.

aasaeoa The above ingredients were placed in a flask and shakencontinuously for hours at room.

temperature. A sample of the resulting resinous. solution, together withthe undissolved matter present therein, was placed on a 140 C.hotplate.-

The resin bodied quickly on the hotplate to an infusible state. Itpossessed excellent cohesive characteristics and could be removed fromthe hotplate in sheet form.

Example 2 g Parts Diamino s-triazinyl carboxy-methyl sulphide 20.0Aqueous formaldehyde (approx. 37.1%

HCHO) 651.8

were heated together under reflux at the boiling temperature of the massfor 5 minutes. The reaction mixture was cooled and filtered. The residuewas washed and dried at room temperature. The resinous condensationproduct of diamino s-triazinyl carboxy-methyl sulphide and formaldehydeproduced in this manner was found to be suitable for use as a curingagent for acidcuring thermosetting resins, as shown by the followingexamples:

Example 3 7 Parts Urea 30.0 Aqueous formaldehyde (approx. 37.1%

HCHO)= 64.8 Aqueous ammonia (approx. 28% NH-a) 3.0 Aqueous solution ofsodium hydroxide 0.5 N) 2.0 Curing agent from Example 2 4.0

were heated together under reflux at the boiling temperature of the massfor minutes. The resulting resinous condensation product was mixed with34 parts alpha cellulose in flock form and 0.2 part of amold lubricant,specifically zinc staarate, to form a molding (moldable) composi- Theresulting wet molding compound was dried at '70 C. until suillcientmoisture had been removed to provide a material that could be moldedsatisfactorily. A sample of thedried and ground molding composition wasmolded for 5 minutes at l i0 C. under a pressure of 6,750 pounds persquare inch. A. well-cured molded article having a well-knit andhomogeneous structure was obtained. The molding compound showed goodplastic flow during molding.

were heated together under reflux at the boilingtemperature of the massfor 12 minutes. A moldv ing compound was made from the resultingresinous syrup by mixing therewith 39' parts alpha cellulose and 0.2part zinc stearate. The wet compound was dried as described underExample 3. A sample of the dried and ground molding composition wasmolded for 5 minutes at 1'40 C. under a pressure of 5,600 pounds persquare inch. The molded piece was removed hot from the mold and did notwarp or become distortcd upon cooling to room temperature. moldedarticle was well cured and had a well- The knit and homogeneousstructure. The molding compound showed good plastic flow during moldingas evidenced by the amount of flash on the molded piece. 5

together under reflux at boiling temperature for minutes. manner wasmixed with 43 parts alpha cellulose and 0.2 part zinc stearate.The'resulting wet 2o molding compound was dried at room temperature. Asample of. the dried and ground compound was molded as described underExample 4, yielding a well-cured and well-knit, homogeneous moldedpiece. The molding compound 26 showed excellent flow characteristicsduring molding.

The following examples illustrate the use of a triazinyl carboxy-alkylsulphide of the kind with which this invention is concerned as a re- 30actant in the preparation of rapidly curing thermosetting resins:Example 6 A syrupy phenolic resin was prepared from the followingcomponents:

The above ingredients were heated with constant stirring at an averagetemperature of 65 C. over a period of 4 hours. The highest temperaturereached during the reaction period was 95 C. and

w the lowest was C. The clear resinous syrup is referred to in thefollowing formula as syrupy phenolic resin:

Parts Syrupy phenolic resin 250.0 50 Diamino s-triazinyl carboxy-methylsulphide 14.3,.

Glycerine 5.0

These ingredients were mixed together and the resulting mixture then wasdehydrated under a 66 over a period of approximately 45-60 minutes. Whenall the water had been removed in this manner, the molasses-like castingresin thereby obtained was poured into a container. The resin was heatedin this container for about 16 hours at 83 C. The resin cured to aninsoluble and infusible state. It was transparent, clear, hard and lightin color.

Example 7 Parts Syrupy phenolic resin such as described under Example 6125.0 Diamino s-triazinyl carboxy-methyi sulphide were heated togetherunder reflux at the boiling,

temperature of the mass for 15 minutes, yielding a clear solution thatshowed some evidence of The resinous syrup produced in this reducedpressure of approximately 30 mm. mercury. During the dehydration periodthe resin temperature was raised slowly to 1l0-115 C.

clouding around the edges of the reaction vessel. The resinouscondensation product thereby obtained was mixed with 44 parts alphacellulose in flock form and 0.2 part zinc stearate. The wet moldingcompound was air-dried and then was ground. A sample of the dried andground compound was molded for 15 minutes at 140 C. under a pressure of6,750 pounds per square inch. A well-cured, well-knit and homogeneousmolded piece was obtained. The molded article showed excellent waterresistance when immersed in boiling water for 15 minutes. The moldingcompound showed very good plastic flow during molding.

Examples 6 and 7 illustrate the fact that the triazinyl carboxy-allwlsulphides herein described are eminently satisfactory for use in curingacidcuring thermosetting resins of the phenoplast' type.

Example 8 Parts Urea 30.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 64.8

Diamino s-triazinyl carboxy-methyl sulphide 0.4

Aqueous ammonia (approx. 28% NH3) 3.0

Aqueous solution of sodium hydroxide were heated together under refluxat the boiling temperature of the mass for 18 minutes. The resultingresinous syrup was mixed. with 33.5 parts alpha cellulose and 0.2 partzinc stearate to form a molding compound. The wet molding compositionwas dried at room temperature. A well-molded piece was produced bymolding a sample of the dried and ground molding compound for minutes at135 C. under a pressure of 3,500 pounds per square inch.

Example 9 Parts Urea 30.0 Aqueous form aldehyde (approx. 37.1

HCHO) 64.8

Diamino s-triazinyl carboxy-methyl sulphide 1.0 Aqueous ammonia (approx.28% NH3) 4.0 Aqueous solution of sodium hydroxide All of the aboveingredients with the exception of the diamino s-triazinyl carboxy-methylsulphide were heated together under reflux at the boiling temperature ofthe mass for 15 minutes. The triazine derivative was now added andrefluxing was continued for an additional 10 minutes to cause thetriazinyl compound to intercondense with the urea-formaldehyde partialcondensation product. A molding compound and a molded article wereproduced as described under- Example 8. The molding composition of thisexample yielded a molded article that was higher in water resistancethan the molded piece of Example 8.

Example 10 Parts Melamine 31.5 Aqueous formaldehyde (approx. 37.1%

HCHO) 60.0

Diamino s-triazinyl carboxy-methyl sulphide 0.4 Aqueous ammonia (approx.28% NHa) 3.2 Aqueous solution of sodium hydroxide All of the aboveingredients with the exception of the sulphide were heated togetherunder reflux at boiling temperature for 17 minutes. The sulphide was nowadded and refluxing was continued for an additional 5 minutes. A moldingcompound was produced from the resulting resinous syrup by mixingtherewith 32.5 parts alpha cellulose and 0.2 part zinc stearate: The wetmolding compound was dried at room temperature. A sample of the driedand ground molding composition was molded for 5 minutes at 135 C. undera pressure of 3,500 pounds per square inch. A well-cured molded piecehaving excellent resistance to water was obtained.

Example 11 Parts Thiourea 38.0 Aqueous formaldehyde (approx. 37 .1

HCHO) 64.8 Diamino s-triazinyl carboxy-methol sulphide 0.4 Aqueousammonia (approx. 28% NHs) 3.8

Aqueous solution of sodium hydroxide All of the above ingredients withthe exception of the diamino s-triazinyl carboxy-methyl sulphide wereheated together under reflux at boiling temperature for 15 minutes. Thesulphide was now added and refluxing was continued for an additional 11minutes. The resulting resinous syrup was mixed with 36.4 parts alphacellulose and 0.2 part zinc stearate. The wet molding compound producedin this manner was dried at room temperature. A well-molded article wasproduced by molding a sample of the dried and ground molding compoundfor 5 minutes at C. under a pressure of 3,500 pounds per square inch.

Example 12 Parts Thiourea 38.0 Aqueous formaldehyde (approx. 37.1

HCHO) 90.0 Diamino s-triazinyl carboxy-methyl sulphide 1.5 Aqueousammonia (approx. 28% NH3) 5.0

Aqueous solution of sodium hydroxide All of the above components withthe exception of the sulphide were heated together under rc-, flux atboiling temperature for 10 minutes. The sulphide was now added andrefluxin was continued for an additional 20 minutes. The resultingresinous syrup was mixed with 45.3 parts alpha cellulose and 0.2 partzinc stearate to form a molding compound. The wet molding compositionwas dried at 70 C A sample of the dried and ground molding compositionwas molded as described under Example 11. The molded piece was wellcured and had very good resistance to water, as shown by the fact thatit absorbed only 2.8% by weight of water when immersed in boiling waterfor 15 minutes followed by immersion in cold water for 5 minutes.

It will be understood, of course, by those skilled in the art that ourinvention is not limited to condensation products obtained by reactionof ingredients comprising an aldehyde and the specific diaminos-triazinyl carboxy-alkyl sulphide named in the above illustrativeexamples. Thus. instead of diamino s-triazinyl carboxy-methyl sulphide,we may use diamino s-triazinyl alpha- (carboxy-ethyl) sulphide or anyother organic essence sulphide (or mixture thereof) of the kind withwhich his invention is concerned, numerous examples of which compoundshave been given hereinbefore and in our copending application Serial No.421,682.

in producing these new condensation products the choice of the aldehydeis dependent largely upon economic considerations and upon'theparticular properties desired in the finished product. We prefer to useas the aldehydic reactant formaldehyde or compounds engenderingformaldehyde, e. g... paraiormaldehyde, hexamethylene tetramine, etc.illustrative examples ofother aldehydes that may he used areacetaldehyde, propionaldehyde, butyraldehyde, acrolein, methacrolein,crotonaldehyde, benzaldehyde, 'furfural, hydronyaldehydes (e. g.,glycollic aldehyde, glyceraldehyde, etc), mixtures thereof, or mixturesoi formaldehyde (or compounds engendering formaldehyde) with suchaldehydes. Illustrative examples oi aldehyde-addition products that maybe employed instead of the aldehydes themselves are the monoandpoly-(N-carbinol) derivatives, more particularly the monoandpoly-methylol derivatives of urea, thiourea, selenourea and iminourea,and of substituted ureas, seieno'iu'eas, thioureas and imiiioureas,monoand poly il l-carbinol) derivatives of amides of polycarboxylicacids, e. g, maleic, itaconic, fuinaric, adipic, malonic, succinic,citric, phthalic, etc, monoand poiyAN-carbinol) derivative of theaminotriazoles, monoand poly-(N-carbinol) derivatives of theamihodiaaines, etc. Particularlygood results are obtained with activemethylene-containing bodies such as a methylol urea, more particularlymonoand di-methylol areas, and a methylol melamine, e, g., monomethylolmelamine and polymethylol melamines (di-, tri-, tetra-, pentaandhexa-methylol melamines). Mixtures of aldehydes and aldehyde-additionproducts may be employed, e. g., mixtures of formaldehyde and. methylolcompounds such, for instance, a dimethylol urea, trimethylol mela mine,hexamethyiol melamine, etc.

lhe ratio of the aldehydic reactant to the triazine derivative may bevaried over a wide range depending upon the particular propertiesdesired in the final product. Thus, we may use, for example, from 0.5 to6 or 7 mols of an aldehyde for each moi of triazine derivative. Thelower amounts are preferred when the reaction product of the aldehydeand triazine derivative are who used as agents for accelerating theconversion of acid-curing thermosetting resins to an insoluble,infusible state. When the aldehyde is available for reaction in the formof. an alkylol derivative, more particularly a methylol derivative such,for instance, as dimethylol urea, trimethylol inelamine, etc, thenhigher amounts of such aldehydeaddition products ordinarily are used,for example, from 1 to 12 or 15 or more-mols of such alkylol derivativesfor each mol of thetriazine derivative.

When the diamino triazinyl carboxy-alkyl sulphide is used primarily asan intercondensable curing reactant for accelerating the conversion ofacid-curing thermosetting resins to an insoluble, infusible state, onlya relatively small amount of such sulphide ordinarily is required, forexample an amount corresponding to from 0.4 or 0.5% to 5 or 6% by weightof the resin to be cured, calculated on the basis of the dry resin- Insome cases it may bedesirable to use higher amounts, for instance up to10 or or more parts by weight lit of the sulphide per 100 parts (netdry) of the acid-curing thermosetting resin. When the sulphide isincorporated into the acid-curing thermosetting resin in the forinof asoluble, fusible aldehyde-reaction product thereof, then higher amountsof such reaction product ordinarily are used as compared with the amountemployed when using the sulphide itself. The sulphide or its partialreaction product with an aldehyde may be incorporated into, theacid-curing thermosetting resin either prior to, during or after theformation of the resin or prior to, during or after the formation of amolding composition containing' the acid-curing thermosetting resin.

' of such sulphides.

Examples of acid-curing thermosetting resins. the curing of whichisaccelerated by the diamino triazinyl carboxy-allryl sulphide hereindescribed or by their soluble, fusible aldehyde-reaction products, arethe acidwuring phenol-aldehyde resins, aminotriazole-aldehyde resins,melamineiormaldehyde resins, urea-aldehyde resins,ureaammotriazine-aldehyde resins, aminodiazine-aldehyde resins,protein-aldehyde resins (e. g, casein-formaldehyde resins), resinouscondensation products of aldehyde such as formaldehyde with polyarnidesas, for instance, malonic diamide, maieic diamide, iumaric diamide,itaconic diamide, etc. Other examples of amino or amide compounds thatmay be condensed with aldehydes such as hereinbefore mentioned by way oiillustration'in forming an acid-curing thermosetting resin, moreparticularly an acid-curing aminoplast, are thiourea, oiurea,diethylenetriurea, methyl urea, acetyl. urea, benzoyl urea, phenyithiourea, asymmetrical diethyl urea, allyl urea, Z-chloroarlyr urea,ethylidene urea, guanyl urea, biguamde, aminoguanidine, melamine,triureido melamine, ammeline, ammelide, melem. melam, melon,aininotriazoies, aminodiazines, etc. Suitable mixtures of such compoundsalso may be used.

Phenol itself and various substituted phenols, for example the cresols,the xylenols, etc., may be condensed with aldehydes, e. g.,formaldehyde, furfural, etc, to form acid-curing thermosetting resins ofthe phenoplast type, and these thermosetting resins then can be Cured toth insoluble and infusible state with the aid of the hereindescribedtriazinyl carboxy-alkyl sulphides or with the soluble, fusiblealdehyde-reaction products The curing agents of this in- 'vention, whenincorporated into acid-curing phenoplasts, also impart improved colorand light stability to the curved product. This was quite unexpected,since in no way could it have been predicted that the introduction ofatriazine de rivative containing an -NHR radical and, also, a --COOHradical into an acid-curing phenoplast would improve the color of theend-prodnot and, in addition, facilitate the conversion of thepotentially reactive resin to a cured (insoluble and infusible) state.Another advantag accruing from our invention resides in the simplicitywith which casting resins. particularly phenol-aldehyde casting resinsadapted to be hardened under heat (e. g., at temperatures of the orderof about 60 to (3.), can be produced. If desired, the fundamental resinsof this invention may be modified by introducing other bodies before,during or after condensation be:

1941, page 3, colunm 2, lines 53-75, page 4, column 1, lines 1-40, whichpatent is assigned to the same assignee as the present invention.

, 'I'hermosetting molding composition comprising a filler and anacid-curing thermosetting resin carrying a curing agent comprising adiamino triazinyl carboxy-alkyl sulphide of the kind herein described,'or a soluble, fusible aldehyde-reaction product of such a sulphide, maybe molded into a variety of shapes under heat and pressure, moreparticularly at temperatures of the order of 100 to 200 0., preferablyfrom approximately 120 to 180 C. The molding compositions show goodplastic flow during molding, since the curing agent not only functionsas such but also generally serves to impart improved plastic flow to themolding composition. Molded articles of manufacture comprising themolded, heat-hardened molding compositions of this invention have a goodsurface finish, show no evidence of bleeding the curing agent, are wellcured throughout, and show no loss in any of their other usefulproperties due to the presence of the triazinyl carboxy-alkyl sulphideor aldehyde-reaction product thereof.

What we claim as new and desire to secure by Letters Patent of theUnited States is:

1. A composition comprising an acid-curing, thermosetting resin carryinga curing agent therefor comprising a compound selected from the classconsisting of (1) compounds represented by the general formula ErnannN-c where n represents an integer and is at least 1 and not more than2, and R represents a member of the class consisting of hydrogen andmonovalent hydrocarbon and halo-hydrocarbon radicals; and (2) soluble,fusible aldehyde-reaction products of the compounds of (1) 2. Acomposition comprising an acid-curing, thermosetting, phenol-aldehyderesin having incorporated therein a compound represented by the generalformula c-scmmooon N ll o-somiocoon N I I where n represents an integerand is at least 1 and not more than 2, and It represents a member of theclass consisting of hydrogen and monovalent hydrocarbon andhalo-hydrocarbon radicals.

4. A composition of matter comprising the product of reaction ofingredients comprising an aldehyde and a compound represented by thegeneral formula NHR where n represents an integer and is at least 1 andnot more than 2, and R represents a member of the class consisting ofhydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

5. A composition as in claim 4 wherein the aldehyde is formaldehyde.

6. A composition comprising the product of reaction of ingredientscomprising an aldehyde and a compound represented by the general formulaWhere n is an integer and is at least 1 and not more than 2.

7. A composition comprising the condensation product of ingredientscomprising formaldehyde and diamino s-triazinyl carboxy methyl sulphide.

8. A composition comprising the product of reaction of ingredientscomprising a phenol, an aldehyde and a compound represented by theeneral formula where n represents an integer and is at least 1 and notmore than 2, and R represents a member of the class consisting ofhydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

9. A composition comprising the product of reaction of ingredientscomprising a urea, an aldehyde and a compound represented by the generalformula NHR where n represents an integer and is at least 1 and not morethan 2, and R represents a member of the class consisting of hydrogenand monovalent hydrocarbon and halo-hydrocarbon radicals.

10. A heat-curable resinous condensation product of ingredientscomprising urea, formaldehyde and a compound represented by the generalformula where n is an integer and is at least 1 and not more than 2. I

11. A product comprising the cured resinous condensation product ofclaim 10. i

12. A composition comprising the resinous product of reaction ofingredients comprising melamine, formaldehyde and a compound representedby the general formula an aldehyde, and (2) a compound represented bythe general formula N t-scrmocoon \N% where n is an integer and isat-least 1 and not more than 2.

14. A composition comprising the resinous product of reaction of (l) apartial condensation product of ingredients comprising a urea and analdehyde, and (2) a compound represented by the general formula BEN-where n is an integer and is at least 1 and not more than 2.

15. A resinous composition comprising the product of reaction of (l) apartial condensat on product obtained by reaction, while admixed with analkaline substance, of ingredients comprising urea and formaldehyde, and(2) diamino s-triazinyl carboxy-methyl sulphide.

16. A resinous composition comprising the product of reaction of- (1) apartial condensation product obtained by reaction, while admixed with analkaline substance, of ingredients comprising melamine and formaldehyde,and (2) diamino s-triazinyl carboxy-methyl sulphide.

17. A composition comprising the resinous product of reaction ofingredients comprising urea, carboxy-methyl sulphide.

18. A thermosetting molding composition comprising a filler and anacid-curing partial condensation product of ingredients comprising ureaand formaldehyde, said condensation product having incorporated thereina small amount of a curing agent comprising diamino s-triazinylcarboxy-methyl sulphide.

19. The method of preparing new condensation products which compriseseffecting reaction between ingredients comprising an aldehyde and acompound represented by the general formula.

where it represents an integer and is at least 1 and not more than 2,and R represents a member of the class consisting of hydrogen andmonovalent hydrocarbon and halo-hydrocarbon radicals.

20. The method which comprises effecting partial reaction betweeningredients comprising urea and formaldehyde under alkaline conditions,addingto the resulting partial condensation product a small amount of acompound represented by the general formula where n represents aninteger and is at least 1 and not more than 2, and causing the saidcompound to intercondense with the said partial condensation product.

GAETANO F. DALELIO. JAMES W. unnnawoon.

formaldehyde and diamino s-triazinyl CERTIFICATE OF CORRECTION. PatentNo. 2,558,h92. January A, 19141;.

GAETANO F. DIALELIO, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,sec-- ond column, line 1, for "ethyl, chlorophenyl, phenyl," read-ethy1chlorophenyl, phenyl-; page 1;, second column, line 21, forzarboxy-methol" read -carboxy-methyi--; page 5, second column, line 17,for "sulphide" read -su1phides-; line 25, for "aldehyde" read--aldehydes--; line 5b., for curved read "cured"; page 7, second column,line 20, after "formula" strike out the period; and that the 'saidLetters Patent should be read with this correction therein that the samemay conform to the record of the case in the Patent Office.

Signed and sealed this 25th day of April, A. 0. 19M

Leslie Frazer (Seal) Acting Commissioner of Patents.

